A RANDOM-MATRIX TRANSITION-STATE THEORY FOR THE PROBABILITY-DISTRIBUTION OF STATE-SPECIFIC UNIMOLECULAR DECAY-RATES - GENERALIZATION TO INCLUDE TOTAL ANGULAR-MOMENTUM CONSERVATION AND OTHER DYNAMICAL SYMMETRIES

被引:57
作者
HERNANDEZ, R
MILLER, WH
MOORE, CB
POLIK, WF
机构
[1] LAWRENCE BERKELEY LAB,DIV CHEM SCI,BERKELEY,CA 94720
[2] HOPE COLL,DEPT CHEM,HOLLAND,MI 49423
关键词
D O I
10.1063/1.465360
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A previously developed random matrix/transition state theory (RM/TST) model for the probability distribution of state-specific unimolecular decay rates has been generalized to incorporate total angular momentum conservation and other dynamical symmetries. The model is made into a predictive theory by using a semiclassical method to determine the transmission probabilities of a nonseparable rovibrational Hamiltonian at the transition state. The overall theory gives a good description of the state-specific rates for the D2CO --> D2 + CO unimolecular decay; in particular, it describes the dependence of the distribution of rates on total angular momentum J. Comparison of the experimental values with results of the RM/TST theory suggests that there is mixing among the rovibrational states.
引用
收藏
页码:950 / 962
页数:13
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